The exploitation of electrocatalysts with high activity and durability for HER is desirable for future energy systems,but it is still a challenge.NMPs have attracted increasing attentions,but the preparation process o...The exploitation of electrocatalysts with high activity and durability for HER is desirable for future energy systems,but it is still a challenge.NMPs have attracted increasing attentions,but the preparation process often needs toxic regents or dangerous reaction conditions.Herein,we develop a general green method to fabricate metal-rich NMPs anchored on NPG through pyrolyzing DNA cross-linked complexes.The obtained Ru_(2) P-NPG exhibits an ultrasmall overpotential of 7 mV at 10 mA cm^(2) and ultralow Tafel slope of 33 mV dec^(-1) in 1.0 mol L?1 KOH,even better than that of commercial Pt/C.In addition,Ru 2 P-NPG also shows low overpotentials of 29 and 78 mV in 0.5 mol L^(-1) H_(2)SO_(4) and 1.0 mol L^(-1) PBS,respectively.The superior activity can be attributed to the ultrafine dispersion of Ru 2 P nanoparticles for more accessible sites,more defects formed for abundant active sites,the two-dimensional plane structure for accelerated electron transfer and mass transport,as well as the regulation of electron distribution of the catalyst.Moreover,the synthetic method can also be applied to prepare other metal-rich noble metal phosphides(Pd_(3)P-NPG and Rh_(2)P-NPG),which also exhibits high activity for HER.This work provides an effective strategy for designing NMP-based electrocatalysts.展开更多
Designing highly active,durable,and nonprecious metal-based bifunctional electrocatalysts for overall water electrolysis is of urgent scientific importance to realize the sustainable hydrogen production,which remains ...Designing highly active,durable,and nonprecious metal-based bifunctional electrocatalysts for overall water electrolysis is of urgent scientific importance to realize the sustainable hydrogen production,which remains a grand challenge.Herein,an innovative approach is demonstrated to synthesize flower-like 3D homogenous trimetallic Mn,Ni,Co phosphide catalysts directly on nickel foam via electrodeposition followed by plasma phosphidation.The electrochemical activity of the catalysts with varying Mn:Ni:Co ratios is assessed to identify the optimal composition,demonstrating that the equimolar trimetallic phosphide yields an outstanding HER catalytic performance with a current density of 10 mA cm^(-2) at an ultra-low overpotential of~14 mV,outperforming the best reported electrocatalysts.This is asserted by the DFT calculations,revealing strong interaction of the metals and the P atom,resulting in enhanced water activation and optimized G_(H)^(*)values for the HER process.Moreover,this optimal composition appreciably catalyzes the OER by exposing more intrinsic active species in-situ formed on the catalyst surface during the OER.Therefore,the Mn_(1)-Ni_(1)-Co_(1)-P-(O)/NF catalyst exhibits a decreased overpotential of~289 mV at 10 mA cm^(-2).More importantly,the electrocatalyst sustains perfect durability up to 48 h at a current density of 10 mA cm^(-2) and continued 5000 cycling stability for both HER and OER.Meanwhile,the assembled MNC-P/NF||MNC-P/NF full water electrolyzer system attains an extremely low cell voltage of 1.48 V at 10 mA cm^(-2).Significantly,the robust stability of the overall system results in a remarkable current retention of~96%after a continuous 50-h run.Therefore,this study provides a facile design and a scalable construction of superb bifunctional ternary MNC-phosphide electrocatalysts for efficient electrochemical energy production systems.展开更多
Transition metal phosphides(TMPs)have been regarded as alternative hydrogen evolution reaction(HER)and oxygen evolution reaction(OER)catalysts owing to their comparable activity to those of noble metal-based catalysts...Transition metal phosphides(TMPs)have been regarded as alternative hydrogen evolution reaction(HER)and oxygen evolution reaction(OER)catalysts owing to their comparable activity to those of noble metal-based catalysts.TMPs have been produced in various morphologies,including hollow and porous nanostructures,which are features deemed desirable for electrocatalytic materials.Templated synthesis routes are often responsible for such morphologies.This paper reviews the latest advances and existing challenges in the synthesis of TMP-based OER and HER catalysts through templated methods.A comprehensive review of the structure-property-performance of TMP-based HER and OER catalysts prepared using different templates is presented.The discussion proceeds according to application,first by HER and further divided among the types of templates used-from hard templates,sacrificial templates,and soft templates to the emerging dynamic hydrogen bubble template.OER catalysts are then reviewed and grouped according to their morphology.Finally,prospective research directions for the synthesis of hollow and porous TMP-based catalysts,such as improvements on both activity and stability of TMPs,design of environmentally benign templates and processes,and analysis of the reaction mechanism through advanced material characterization techniques and theoretical calculations,are suggested.展开更多
Supercapacitors(SCs)are considered promising energy storge systems because of their outstanding power density,fast charge and discharge rate and long-term cycling stability.The exploitation of cheap and efficient elec...Supercapacitors(SCs)are considered promising energy storge systems because of their outstanding power density,fast charge and discharge rate and long-term cycling stability.The exploitation of cheap and efficient electrode materials is the key to improve the performance of supercapacitors.As the battery-type materials,transition metal phosphides(TMPs)possess high theoretical specific capacity,good electrical conductivity and superior structural stability,which have been extensively studied to be electrode materials for supercapacitors.In this review,we summarize the up-to-date progress on TMPs materials from diversified synthetic methods,diverse nanostructures and several prominent TMPs and their composites in application of supercapacitors.In the end,we also propose the remaining challenges toward the rational discovery and synthesis of high-performance TMP electrodes materials for energy storage.展开更多
The controllable and safe hydrogen storage technologies are widely recognized as the main bottleneck for the accomplishment of sustainable hydrogen energy.Ammonia borane(AB)has regarded as a competitive candidate for ...The controllable and safe hydrogen storage technologies are widely recognized as the main bottleneck for the accomplishment of sustainable hydrogen energy.Ammonia borane(AB)has regarded as a competitive candidate for chemical hydrogen storage.However,developing efficient yet high-performance catalysts towards hydrogen evolution from AB hydrolysis remains an enormous challenge.Herein,cobalt phosphide nanosheets are synthesized by a facile salt-assisted along with low-temperature phosphidation strategy for simultaneously modulating its morphology and electronic structure,and function as hydrogen evolution photocatalysts.Impressively,the Co_(2)P nanosheets display extraordinary performance with a record high turnover frequency of 44.9 min^(-1),outperforming most of the noble-metal-free catalysts reported to date.This remarkable performance is attributed to its desired nanosheets structure,featuring with high specific surface area,abundant exposed active sites,and short charge diffusion paths.Our findings provide a novel strategy for regulating metal phosphides with desired phase structure and morphology for energy-related applications and beyond.展开更多
Boron phosphide(BP)has gained significant research attention due to its unique photoelectric and mechanical properties.In this work,we investigated the stability of BP under high pressure using x-ray diffraction and s...Boron phosphide(BP)has gained significant research attention due to its unique photoelectric and mechanical properties.In this work,we investigated the stability of BP under high pressure using x-ray diffraction and scanning electron microscope.The phase diagram of BP was explored in both B-rich and P-rich environments,revealing crucial insight into its behavior at 5.0 GPa.Additionally,we measured the melting curve of BP from 8.0 GPa to 15.0 GPa.Our findings indicate that the stability of BP under high pressure is improved within B-rich and P-rich environments.Furthermore,we report a remarkable observation of melting curve frustration at 10.0 GPa.This study will enhance our understanding of stability of BP under high pressure,shedding light on its potential application in semiconductor,thermal,and light-transmitting devices.展开更多
SiO2-supported Ni-Mo bimetallic phosphides were prepared by temperature-programmed reduction (TPR) method from the phosphate precur- sors calcined at different temperatures. Their properties were characterized by me...SiO2-supported Ni-Mo bimetallic phosphides were prepared by temperature-programmed reduction (TPR) method from the phosphate precur- sors calcined at different temperatures. Their properties were characterized by means of ultraviolet-visible diffuse reflectance spectroscopy (UV-Vis DRS), H2 temperature-programmed reduction (H2-TPR), X-ray diffraction (XRD), transmission electron microscopy (TEM), CO chemisorption, H2 and NH3 temperature-programmed desorptions (H2-TPD and NH3-TPD). Their catalytic performances for the deoxygena- tion of methyl laurate were tested in a fixed-bed reactor. When the precursors were calcined at 400 and 500 ℃, respectively, NiMoP2 phase could be formed apart from Ni2P and MoP phases in the prepared C400 and C500 catalysts. However, when the precursors were calcined at 600, 700 and 800 ℃, respectively, only Ni2P and MoP phases could be detected in the prepared C600, C700 and C800 catalysts. Also, in C400, C500 and C600 catalysts, Mo atoms were found to be entered in the lattice of Ni2P phase, but the entering extent became less with the increase of calcination temperature. As the calcination temperature of the precursor increased, the interaction between Ni and Mo in the prepared catalysts decreased, and the phosphide crystallite size tended to increase, subsequently leading to the decrease in the surface metal site density and the acid amount. C600 catalyst showed the highest activity among the tested ones for the deoxygenation of methyl laurate. As the calcination temperature of the precursor increased, the selectivity to C12 hydrocarbons decreased while the selectivity to C11 hydrocarbons tended to increase. This can be mainly attributed to the decreased Ni-Mo interaction and the increased phosphide particle size. In sum, the structure and performance of Ni-Mo bimetallic phosphide catalyst can be tuned by the calcination temperature of precursor.展开更多
Wearable supercapacitors(SCs)are gaining prominence as portable energy storage devices.To develop high-performance wearable SCs,the significant relationship among material,structure,and performance inspired us with a ...Wearable supercapacitors(SCs)are gaining prominence as portable energy storage devices.To develop high-performance wearable SCs,the significant relationship among material,structure,and performance inspired us with a delicate design of the highly wearable embroidered supercapacitors made from the conductive fibers composited.By rendering the conductive interdigitally patterned embroidery as both the current collector and skeleton for the SCs,the novel pseudocapacitive material cobalt phosphides were then successfully electrodeposited,forming the first flexible and wearable in-plane embroidery SCs.The electrochemical measurements manifested that the highest specific capacitance was nearly 156.6 mF cm?2(65.72 F g?1)at the current density of 0.6 mA cm?2(0.25 A g?1),with a high energy density of 0.013 mWh cm?2(5.55 Wh kg?1)at a power density of 0.24 mW cm?2(100 W kg?1).As a demonstration,a monogrammed pattern was ingeniously designed and embroidered on the laboratory gown as the wearable in-plane SCs,which showed both decent electrochemical performance and excellent flexibility.展开更多
Li-S batteries have been considered as one of advanced next-generation energy storage systems owing to their remarkable theoretical capacity(1672 m Ah g^(-1))and high energy density(2600 Wh kg^(-1)).However,critical i...Li-S batteries have been considered as one of advanced next-generation energy storage systems owing to their remarkable theoretical capacity(1672 m Ah g^(-1))and high energy density(2600 Wh kg^(-1)).However,critical issues,mainly pertaining to lithium polysulfide shuttle and slow sulfur reaction kinetics,have posed a fatal threat to the electrochemical performances of Li-S batteries.The situation is even worse for high sulfur-loaded and flexible cathodes,which are the essential components for practical Li-S batteries.In response,the use of metal compounds as electrocatalysts in Li-S systems have been confirmed as an effective strategy to date.Particularly,recent years have witnessed many progresses in phosphidesoptimized Li-S chemistry.This has been motivated by the superior electron conductivity and high electrocatalytic activity of phosphides.In this tutorial review,we offer a systematic summary of active metal phosphides as promoters for Li-S chemistry,aiming at helping to understanding the working mechanism of phosphide electrocatalysts and guiding the construction of advanced Li-S batteries.展开更多
Transition metal phosphides are a class of promising electrocatalysts for hydrogen evolution reaction(HER) to replace noble metals.In this work,we for the first time synthesize carbon supported CoP nanoparticles with ...Transition metal phosphides are a class of promising electrocatalysts for hydrogen evolution reaction(HER) to replace noble metals.In this work,we for the first time synthesize carbon supported CoP nanoparticles with the average particle sizes from 3.3 to 9.2 nm,via a solvothermal process followed by low-temperature topological phosphorization,and the size-dependent HER activity of the CoP is investigated by virtue of TEM,XRD,XPS and the electrochemical techniques.It is discovered that the 9.2nm-CoP particles possess high intrinsic HER catalytic activity as compared to the 3.3nm-CoP,although the smaller one displays a high mass activity due to the large surface area.Detailed studies manifest that the small CoP particles suffer from serious oxidation once exposing to air.In contrast,most cobalt remains in the quasi-metallic state in the relatively large CoP particles,which is beneficial for the desorption of Hads,the rate determining step of the HER process over CoP surface.In addition,the low charge transfer resistance across the liquid/solid interfaces also contributes to the excellent HER activity of the relatively large CoP particles.展开更多
Among the sustainable energy sources,hydrogen is the one most promising for alleviating the pollution issues related to the usage of conventional fuels,as it can be produced in an efficient and eco-friendly way via el...Among the sustainable energy sources,hydrogen is the one most promising for alleviating the pollution issues related to the usage of conventional fuels,as it can be produced in an efficient and eco-friendly way via electrocatalytic water splitting.The hydrogen evolution reaction(HER,a half-reaction of water splitting)plays a pivotal role in decreasing the price and increasing the catalytic efficiency of hydrogen production and is efficiently promoted by metal phosphides in different electrolytes.Herein,we summarize the recent advances in the development of metal phosphides as HER electrocatalysts,focus on their synthesis(post-treatment,in situ generation,and electrodeposition methods)and the enhancement of their electrocatalytic activity(via elemental doping,interface and vacancy engineering,construction of specific supports and nanostructures,and the design of bior polymetallic phosphides),and highlight the crucial issues and challenges of future development.展开更多
It is critical to synthesize high-efficiency electrocatalysts to boost the performance of water splitting to meet the requirements of industrial applications. Metal-organic frameworks(MOFs) can function as ideal molec...It is critical to synthesize high-efficiency electrocatalysts to boost the performance of water splitting to meet the requirements of industrial applications. Metal-organic frameworks(MOFs) can function as ideal molecular platforms for the design of highly reactive transition metal phosphides(TMPs), a kind of candidates for high-efficiently electrocatalytic water splitting. The intrinsic activity of the electrocatalysts can be greatly improved via modulating the electronic structure of the catalytic center through the MOF precursors/templates. Moreover, the carbon layer converted in-situ by the organic ligands can not only protect the TMPs from being degraded in the harsh electrochemical environments, but also avoid agglomeration of the catalysts, thereby promoting their activities and stabilities. Furthermore,heteroatom-containing ligands can incorporate N, S or P, etc. atoms into the carbon matrixes after conversion, regulating the coordination microenvironments of the active centers as well as their electronic structures. In this review, we first summarized the latest developments in MOF-derived TMPs by the unique advantages in metal, organic ligand, and morphology regulations for electrocatalytic water splitting. Secondly, we concluded the critical scientific issues currently facing for designing state-of-the-art TMP-based electrocatalysts. Finally, we presented an outlook on this research area, encompassing electrocatalyst construction, catalytic mechanism research, etc.展开更多
Thioetherification between mercaptan and diolefin is an efficient process to remove mercaptans in FCC gasoline at mild condition, during which the selective hydrogenation of diolefin to monoolefin is also expected. He...Thioetherification between mercaptan and diolefin is an efficient process to remove mercaptans in FCC gasoline at mild condition, during which the selective hydrogenation of diolefin to monoolefin is also expected. Here, Si O2 supported transition metal(Fe, Co, Ni, Mo and W) phosphides were tested for the thioetherification of isoprene and butanethiol on a fixed-bed reactor at 120℃ and 1.5 MPa H2, and their structure before and after reaction was characterized by means of XRD, HRTEM, N2 sorption, CO chemisorption, NH3-TPD, XPS and TG. It was found that, among different metal phosphides, Mo P/Si O2 showed the best performance, and the optimal nominal Mo P loading was 25%. Apart from the nature of metal, the density of metal and acid sites determined the catalyst performance. Metal site was mainly responsible for hydrogenation of isoprene, while acid site dominantly contributed to the thioetherification and the polymerization of olefins. Moreover, a balance between metallic and acidic functions is required to arrive at a desired performance. Excessive metal sites or acid sites led to the over-hydrogenation of isoprene or the severe polymerization of olefins, respectively. 25%Mo P/Si O2 was tested for 37 h time on stream, and butanethiol conversion maintained at 100%; although isoprene conversion remarkably decreased, the selectivity to isopentenes exceeded 80% after reaction for 11 h. We suggest that the deactivation of Mo P/Si O2 is mainly ascribed to the butanethiol poisoning and the carbonaceous deposit, especially the former.展开更多
Metal-organic frameworks(MOFs)with high porosity and variable structure have attracted extensive attention in the field of electrochemistry,but their poor conductivity and stability have limited their development.Mate...Metal-organic frameworks(MOFs)with high porosity and variable structure have attracted extensive attention in the field of electrochemistry,but their poor conductivity and stability have limited their development.Materials derived from MOFs can maintain the structural diversity and porosity characteristics of MOFs while improving their electrical conductivity and stability.Metal phosphides play an important role in electrochemistry because they possess rich active sites,unique physicochemical properties,and a porous structure.Published results show that MOF-derived metal-phosphides materials have great promise in the field of electrochemistry due to their controllable structure,high specific surface area,high stability and excellent electrical conductivity.MOF-derived metal-phosphides with significant electrochemical properties can be obtained by simply,economical and scalable synthetic methods.This work reviews the application of MOF-derived metal phosphides in electrochemistry.Specifically,the synthesis methodology and morphological characterization of MOFs derived metal-phosphides and their application in electrochemistry are described.Based on recent scientific advances,we discuss the challenges and opportunities for future research on MOF-derived metal-phosphides materials.展开更多
Lithium−sulfur batteries are one of the most competitive high-energy batteries due to their high theoretical energy density of _(2)600 W·h·kg^(−1).However,their commercialization is limited by poor cycle sta...Lithium−sulfur batteries are one of the most competitive high-energy batteries due to their high theoretical energy density of _(2)600 W·h·kg^(−1).However,their commercialization is limited by poor cycle stability mainly due to the low intrinsic electrical conductivity of sulfur and its discharged products(Li_(2)S_(2)/Li_(2)S),the sluggish reaction kinetics of sulfur cathode,and the“shuttle effect”of soluble intermediate lithi-um polysulfides in ether-based electrolyte.To address these challenges,catalytic hosts have recently been introduced in sulfur cathodes to en-hance the conversion of soluble polysulfides to the final solid products and thus prevent the dissolution and loss of active-sulfur material.In this review,we summarize the recent progress on the use of metal phosphides and borides of different dimensions as the catalytic host of sulfur cathodes and demonstrate the catalytic conversion mechanism of sulfur cathodes with the help of metal phosphides and borides for high-en-ergy and long-life lithium-sulfur batteries.Finally,future outlooks are proposed on developing advanced catalytic host materials to improve battery performance.展开更多
Exploring nonprecious electrocatalysts for water splitting with high efficiency and durability is critically important.Herein,bimetallic phosphides are encapsulated into graphitized carbon to construct a C@NiCoP compo...Exploring nonprecious electrocatalysts for water splitting with high efficiency and durability is critically important.Herein,bimetallic phosphides are encapsulated into graphitized carbon to construct a C@NiCoP composite nanoarray using bimetallic metal-organic framework(MOF) as a self-sacrificial template.The resulting C@NiCoP exhibits superior performance for pH-universal electrocatalytic hydrogen evolution reaction(HER),particularly representing a low overpotential of 46.3 mV at 10 mA cm^(-2) and Tafel slope of 44.1 mV dec^(-1) in alkaline media.The structural characterizations combined with theoretical calculation demonstrate that tailored electronic structure from bimetal atoms and the synergistic effect with graphitized carbon layer could jointly optimize the adsorption ability of hydrogen on active sites in HER process,and enhance the electrical conductivity as well.In addition,the carbon layer served as a protecting shell also prevents highly dispersed NiCoP components from agglomeration and/or loss in harsh media,finally improving the durability.This work thus provides a new insight into optimizing activity and stability of pH-universal electrocatalysts by the nanostructural design and electronic structure modulation.展开更多
Developing high-efficiency electrocatalysts for hydrogen evolution reaction(HER) and oxygen evolution reaction(OER) is required to enhance the sluggish kinetics of water dissociation and optimize the adsorption free e...Developing high-efficiency electrocatalysts for hydrogen evolution reaction(HER) and oxygen evolution reaction(OER) is required to enhance the sluggish kinetics of water dissociation and optimize the adsorption free energy of reaction intermediates.Herein,we tackle this challenge by incorporating high-valence Zr into CoP(ZrxCo_(1-x)P),which significantly accelerates the elementary steps of water electrolysis.Theoretical calculations indicate that the appropriate Zr incorporation effectively expedites the sluggish H2O dissociation kinetics and optimizes the adsorption energy of reaction intermediates for boosting the alkaline water electrolysis.These are confirmed by the experimental results of Zr_(0.06)Co_(0.94)P catalyst that delivers exceptional electrochemical activity.The overpotentials at the current density of 10 mA cm^(-2)(j10) are only 62(HER) and 240 mV(OER) in alkaline media.Furthermore,the Zr_(0.06)Co_(0.94)P/CC‖Zr_(0.06)Co_(0.94)P/CC system exhibits superior overall water splitting activity(1.53 V/j10),surpassing most of the reported bifunctional catalysts.This high-valence Zr incorporation and material design methods explore new avenues for realizing high-performance non-noble metal electrocatalysts.展开更多
NiCo-based superalloys exhibit higher strength and creep resistance over conventional superalloys.Compositional effects on elastic properties of the γ and γ' phases in newly-developed NiCo-based superalloys were...NiCo-based superalloys exhibit higher strength and creep resistance over conventional superalloys.Compositional effects on elastic properties of the γ and γ' phases in newly-developed NiCo-based superalloys were investigated by first-principles calculation combined with special quasi-random structures.The lattice constant,bulk modulus,and elastic constants vary linearly with the Co concentration in the NiCo solution.In the selected(Ni,Co)3(Al,W)and(Ni,Co)3(Al,Ti)model γ' phase,the lattice constant,and bulk modulus show a linear trend with alloying element concentrations.The addition of Co,Ti,and W can regulate lattice mismatch and increase the bulk modulus,simultaneously.W-addition shows excellent performance in strengthening the elastic properties in the γ' phase.Systems become unstable with higher W and Ni contents,e.g.,(Ni0.75Co0.25)3(Al0.25 W0.75),and become brittle with higher W and Co addition,e.g.,Co3(Al0.25 W0.75).Furthermore,Co,Ti,and W can increase the elastic constants on the whole,and such high elastic constants always correspond to a high elastic modulus.The anisotropy index always corresponds to the nature of Young's modulus in a specific direction.展开更多
Exploring feasible synthesis approaches to highly efficient and robust bifunctional electrocatalysts toward both oxygen evolution reaction(OER)and oxygen reduction reaction(ORR)is triggering researcher’s even-increas...Exploring feasible synthesis approaches to highly efficient and robust bifunctional electrocatalysts toward both oxygen evolution reaction(OER)and oxygen reduction reaction(ORR)is triggering researcher’s even-increasing interest in rechargeable Zn-air batteries.Herein,sulfur-doped bimetal FeCo phosphide nanoparticles dispersed on N,P,S-tri-doped graphene(donated as S-FeCo3P/NPSG)are rationally prepared through a controllable one-step carbothermal-phosphorization strategy.The modified charge distribution and electron-donor properties of S-FeCo3P/NPSG caused by S decoration render a significantly beneficial effect on the electrocatalytic activities.Consequently,the S-FeCo3P/NPSG electrode exhibits extraordinary bifunctional activities toward oxygen electrochemistry of the OER overpotential of 290 m V at 10 m A cm^(-2) and the ORR half-wave potential of 0.83 V,approaching to that of noblemetal IrO_(2)(289 m V)and Pt/C(0.84 V),respectively,but with more stronger operation stability in alkaline media.When S-FeCo3P/NPSG serves as the air cathode for liquid-state Zn-air battery,the large peak power density and energy density,as well as superb discharge-charge durability(cycling life>600 h)of this device are obtained.Furthermore,all-solid-state Zn-air battery with S-FeCo3P/NPSG as air electrode also displays excellent mechanical flexibility,high power density and stable cycling stability.The self-reconstruction behavior of the S-FeCo3P/NPSG cathode catalysts is also investigated during the electrocatalytic Zn-air battery operation.This work would provide some novel inspiration from aspects of bonding and charge distribution for the rational construction of active and cost-efficient bifucntional oxygen electrocatalysts for energy storage and conversion devices.展开更多
Although conducting materials such as carbon nanotube and carbon fiber paper(CFP)have been extensively employed as support of electrocatalytic active sites,most of them are of poor catalytic functionality by themselve...Although conducting materials such as carbon nanotube and carbon fiber paper(CFP)have been extensively employed as support of electrocatalytic active sites,most of them are of poor catalytic functionality by themselves and undesirable stability during strong acid/alkaline environments or oxidation process.Here we report a novel one-dimensional(1D)nickel phosphide polymorphic heterostructure(denoted as NPPH)to work as one effective carbon-free functional support for loading of single-atom Ir water oxidation electrocatalyst.Specifically,the NPPH composed of both Ni12P5and Ni2P phases is not only active for robust alkaline water oxidation but also is of good stability and hydrophilicity for favorable loading of single-atom dispersed iridium.The NPPH supported single-atom Ir electrocatalyst(Ir/NPPH)is found to exhibit remarkably superior water oxidation activity with respect to the NPPH itself or CFP supported single-atom Ir catalyst(Ir/CFP),demonstrating the synergetic promotion effect between NPPH and single-atom Ir catalyst.Furthermore,the NPPH supported single-atom Ir catalyst can bear alkaline water oxidation for over 120 h at current density of 50 mA cm^(-2).The NPPH developed here is expected as functional support to composite with other water oxidation catalysts,as may be an alternative strategy of developing highly efficient carbon-free electrocatalysts.展开更多
基金This work was supported by the Fundamental Research Funds for the Central Universities(No.2022XJHH02)the National Key Research and Development Program of China(No.2019YFC1907602).
文摘The exploitation of electrocatalysts with high activity and durability for HER is desirable for future energy systems,but it is still a challenge.NMPs have attracted increasing attentions,but the preparation process often needs toxic regents or dangerous reaction conditions.Herein,we develop a general green method to fabricate metal-rich NMPs anchored on NPG through pyrolyzing DNA cross-linked complexes.The obtained Ru_(2) P-NPG exhibits an ultrasmall overpotential of 7 mV at 10 mA cm^(2) and ultralow Tafel slope of 33 mV dec^(-1) in 1.0 mol L?1 KOH,even better than that of commercial Pt/C.In addition,Ru 2 P-NPG also shows low overpotentials of 29 and 78 mV in 0.5 mol L^(-1) H_(2)SO_(4) and 1.0 mol L^(-1) PBS,respectively.The superior activity can be attributed to the ultrafine dispersion of Ru 2 P nanoparticles for more accessible sites,more defects formed for abundant active sites,the two-dimensional plane structure for accelerated electron transfer and mass transport,as well as the regulation of electron distribution of the catalyst.Moreover,the synthetic method can also be applied to prepare other metal-rich noble metal phosphides(Pd_(3)P-NPG and Rh_(2)P-NPG),which also exhibits high activity for HER.This work provides an effective strategy for designing NMP-based electrocatalysts.
文摘Designing highly active,durable,and nonprecious metal-based bifunctional electrocatalysts for overall water electrolysis is of urgent scientific importance to realize the sustainable hydrogen production,which remains a grand challenge.Herein,an innovative approach is demonstrated to synthesize flower-like 3D homogenous trimetallic Mn,Ni,Co phosphide catalysts directly on nickel foam via electrodeposition followed by plasma phosphidation.The electrochemical activity of the catalysts with varying Mn:Ni:Co ratios is assessed to identify the optimal composition,demonstrating that the equimolar trimetallic phosphide yields an outstanding HER catalytic performance with a current density of 10 mA cm^(-2) at an ultra-low overpotential of~14 mV,outperforming the best reported electrocatalysts.This is asserted by the DFT calculations,revealing strong interaction of the metals and the P atom,resulting in enhanced water activation and optimized G_(H)^(*)values for the HER process.Moreover,this optimal composition appreciably catalyzes the OER by exposing more intrinsic active species in-situ formed on the catalyst surface during the OER.Therefore,the Mn_(1)-Ni_(1)-Co_(1)-P-(O)/NF catalyst exhibits a decreased overpotential of~289 mV at 10 mA cm^(-2).More importantly,the electrocatalyst sustains perfect durability up to 48 h at a current density of 10 mA cm^(-2) and continued 5000 cycling stability for both HER and OER.Meanwhile,the assembled MNC-P/NF||MNC-P/NF full water electrolyzer system attains an extremely low cell voltage of 1.48 V at 10 mA cm^(-2).Significantly,the robust stability of the overall system results in a remarkable current retention of~96%after a continuous 50-h run.Therefore,this study provides a facile design and a scalable construction of superb bifunctional ternary MNC-phosphide electrocatalysts for efficient electrochemical energy production systems.
基金the support from the CIPHER Project(IIID 2018-008)funded by the Commission on Higher Education-Philippine California Advanced Research Institutes(CHED-PCARI)。
文摘Transition metal phosphides(TMPs)have been regarded as alternative hydrogen evolution reaction(HER)and oxygen evolution reaction(OER)catalysts owing to their comparable activity to those of noble metal-based catalysts.TMPs have been produced in various morphologies,including hollow and porous nanostructures,which are features deemed desirable for electrocatalytic materials.Templated synthesis routes are often responsible for such morphologies.This paper reviews the latest advances and existing challenges in the synthesis of TMP-based OER and HER catalysts through templated methods.A comprehensive review of the structure-property-performance of TMP-based HER and OER catalysts prepared using different templates is presented.The discussion proceeds according to application,first by HER and further divided among the types of templates used-from hard templates,sacrificial templates,and soft templates to the emerging dynamic hydrogen bubble template.OER catalysts are then reviewed and grouped according to their morphology.Finally,prospective research directions for the synthesis of hollow and porous TMP-based catalysts,such as improvements on both activity and stability of TMPs,design of environmentally benign templates and processes,and analysis of the reaction mechanism through advanced material characterization techniques and theoretical calculations,are suggested.
基金supported by National Undergraduate Training Programs for Innovations[grant number 202210225259]the Outstanding Youth Project of Natural Science Foundation in Heilongjiang Province(YQ2022E040)+3 种基金the Shandong Provincial Natural Science Foundation(ZR2022ME166)the Postdoctoral Scientific Research Developmental Fund of Heilongjiang Province(LBH-Q20023)the University Nursing Program for Young Scholars with Creative Talents in Heilongjiang Province(UNPYSCT-2020197)the 111 Project(B20088).
文摘Supercapacitors(SCs)are considered promising energy storge systems because of their outstanding power density,fast charge and discharge rate and long-term cycling stability.The exploitation of cheap and efficient electrode materials is the key to improve the performance of supercapacitors.As the battery-type materials,transition metal phosphides(TMPs)possess high theoretical specific capacity,good electrical conductivity and superior structural stability,which have been extensively studied to be electrode materials for supercapacitors.In this review,we summarize the up-to-date progress on TMPs materials from diversified synthetic methods,diverse nanostructures and several prominent TMPs and their composites in application of supercapacitors.In the end,we also propose the remaining challenges toward the rational discovery and synthesis of high-performance TMP electrodes materials for energy storage.
基金supported by the National Natural Science Foundation of China(22108238,21878259)the Zhejiang Provincial Natural Science Foundation of China(LR18B060001)+5 种基金Anhui Provincial Natural Science Founda-tion(1908085QB68)the Natural Science Foundation of the Anhui Higher Education Institutions of China(KJ2020A0275)Major Science and Technology Project of Anhui Province(201903a05020055)Foundation of Zhejiang Provincial Key Laboratory of Advanced Chemical Engineering Manufacture Technology(ZJKL-ACEMT-1802)China Postdoctoral Science Foundation(2019M662060,2020T130580)Jiangsu Key Laboratory of Advanced Catalytic Materials and Technology(BM2012110).
文摘The controllable and safe hydrogen storage technologies are widely recognized as the main bottleneck for the accomplishment of sustainable hydrogen energy.Ammonia borane(AB)has regarded as a competitive candidate for chemical hydrogen storage.However,developing efficient yet high-performance catalysts towards hydrogen evolution from AB hydrolysis remains an enormous challenge.Herein,cobalt phosphide nanosheets are synthesized by a facile salt-assisted along with low-temperature phosphidation strategy for simultaneously modulating its morphology and electronic structure,and function as hydrogen evolution photocatalysts.Impressively,the Co_(2)P nanosheets display extraordinary performance with a record high turnover frequency of 44.9 min^(-1),outperforming most of the noble-metal-free catalysts reported to date.This remarkable performance is attributed to its desired nanosheets structure,featuring with high specific surface area,abundant exposed active sites,and short charge diffusion paths.Our findings provide a novel strategy for regulating metal phosphides with desired phase structure and morphology for energy-related applications and beyond.
基金Project supported by the National Natural Science Foundation of China (Grant No.12074273)the Sichuan Science and Technology Program (Grant No.2022NSFSC1810)。
文摘Boron phosphide(BP)has gained significant research attention due to its unique photoelectric and mechanical properties.In this work,we investigated the stability of BP under high pressure using x-ray diffraction and scanning electron microscope.The phase diagram of BP was explored in both B-rich and P-rich environments,revealing crucial insight into its behavior at 5.0 GPa.Additionally,we measured the melting curve of BP from 8.0 GPa to 15.0 GPa.Our findings indicate that the stability of BP under high pressure is improved within B-rich and P-rich environments.Furthermore,we report a remarkable observation of melting curve frustration at 10.0 GPa.This study will enhance our understanding of stability of BP under high pressure,shedding light on its potential application in semiconductor,thermal,and light-transmitting devices.
基金supported by the National Natural Science Foundation of China(No.21176177)the Natural Science Foundation of Tianjin(No.12JCYBJC13200)State Key Laboratory of Catalytic Materials and Reaction Engineering(RIPP,SINOPEC)
文摘SiO2-supported Ni-Mo bimetallic phosphides were prepared by temperature-programmed reduction (TPR) method from the phosphate precur- sors calcined at different temperatures. Their properties were characterized by means of ultraviolet-visible diffuse reflectance spectroscopy (UV-Vis DRS), H2 temperature-programmed reduction (H2-TPR), X-ray diffraction (XRD), transmission electron microscopy (TEM), CO chemisorption, H2 and NH3 temperature-programmed desorptions (H2-TPD and NH3-TPD). Their catalytic performances for the deoxygena- tion of methyl laurate were tested in a fixed-bed reactor. When the precursors were calcined at 400 and 500 ℃, respectively, NiMoP2 phase could be formed apart from Ni2P and MoP phases in the prepared C400 and C500 catalysts. However, when the precursors were calcined at 600, 700 and 800 ℃, respectively, only Ni2P and MoP phases could be detected in the prepared C600, C700 and C800 catalysts. Also, in C400, C500 and C600 catalysts, Mo atoms were found to be entered in the lattice of Ni2P phase, but the entering extent became less with the increase of calcination temperature. As the calcination temperature of the precursor increased, the interaction between Ni and Mo in the prepared catalysts decreased, and the phosphide crystallite size tended to increase, subsequently leading to the decrease in the surface metal site density and the acid amount. C600 catalyst showed the highest activity among the tested ones for the deoxygenation of methyl laurate. As the calcination temperature of the precursor increased, the selectivity to C12 hydrocarbons decreased while the selectivity to C11 hydrocarbons tended to increase. This can be mainly attributed to the decreased Ni-Mo interaction and the increased phosphide particle size. In sum, the structure and performance of Ni-Mo bimetallic phosphide catalyst can be tuned by the calcination temperature of precursor.
基金The Hong Kong Polytechnic University for the funding support(Nos.1-YW1B,G-YBV2,and G-UACC).
文摘Wearable supercapacitors(SCs)are gaining prominence as portable energy storage devices.To develop high-performance wearable SCs,the significant relationship among material,structure,and performance inspired us with a delicate design of the highly wearable embroidered supercapacitors made from the conductive fibers composited.By rendering the conductive interdigitally patterned embroidery as both the current collector and skeleton for the SCs,the novel pseudocapacitive material cobalt phosphides were then successfully electrodeposited,forming the first flexible and wearable in-plane embroidery SCs.The electrochemical measurements manifested that the highest specific capacitance was nearly 156.6 mF cm?2(65.72 F g?1)at the current density of 0.6 mA cm?2(0.25 A g?1),with a high energy density of 0.013 mWh cm?2(5.55 Wh kg?1)at a power density of 0.24 mW cm?2(100 W kg?1).As a demonstration,a monogrammed pattern was ingeniously designed and embroidered on the laboratory gown as the wearable in-plane SCs,which showed both decent electrochemical performance and excellent flexibility.
基金supported by the Project of State Key Laboratory of Environment-Friendly Energy Materials(SWUST,China,Grant Nos.19FKSY16 and 18ZD320304)。
文摘Li-S batteries have been considered as one of advanced next-generation energy storage systems owing to their remarkable theoretical capacity(1672 m Ah g^(-1))and high energy density(2600 Wh kg^(-1)).However,critical issues,mainly pertaining to lithium polysulfide shuttle and slow sulfur reaction kinetics,have posed a fatal threat to the electrochemical performances of Li-S batteries.The situation is even worse for high sulfur-loaded and flexible cathodes,which are the essential components for practical Li-S batteries.In response,the use of metal compounds as electrocatalysts in Li-S systems have been confirmed as an effective strategy to date.Particularly,recent years have witnessed many progresses in phosphidesoptimized Li-S chemistry.This has been motivated by the superior electron conductivity and high electrocatalytic activity of phosphides.In this tutorial review,we offer a systematic summary of active metal phosphides as promoters for Li-S chemistry,aiming at helping to understanding the working mechanism of phosphide electrocatalysts and guiding the construction of advanced Li-S batteries.
基金financially supported by the National Natural Science Foundation of China(21576258,21776146)the Key Research and Development Project of Shandong Province(2018GGX102036)Taishan Scholar Program of Shandong Province(ts201712046)。
文摘Transition metal phosphides are a class of promising electrocatalysts for hydrogen evolution reaction(HER) to replace noble metals.In this work,we for the first time synthesize carbon supported CoP nanoparticles with the average particle sizes from 3.3 to 9.2 nm,via a solvothermal process followed by low-temperature topological phosphorization,and the size-dependent HER activity of the CoP is investigated by virtue of TEM,XRD,XPS and the electrochemical techniques.It is discovered that the 9.2nm-CoP particles possess high intrinsic HER catalytic activity as compared to the 3.3nm-CoP,although the smaller one displays a high mass activity due to the large surface area.Detailed studies manifest that the small CoP particles suffer from serious oxidation once exposing to air.In contrast,most cobalt remains in the quasi-metallic state in the relatively large CoP particles,which is beneficial for the desorption of Hads,the rate determining step of the HER process over CoP surface.In addition,the low charge transfer resistance across the liquid/solid interfaces also contributes to the excellent HER activity of the relatively large CoP particles.
文摘Among the sustainable energy sources,hydrogen is the one most promising for alleviating the pollution issues related to the usage of conventional fuels,as it can be produced in an efficient and eco-friendly way via electrocatalytic water splitting.The hydrogen evolution reaction(HER,a half-reaction of water splitting)plays a pivotal role in decreasing the price and increasing the catalytic efficiency of hydrogen production and is efficiently promoted by metal phosphides in different electrolytes.Herein,we summarize the recent advances in the development of metal phosphides as HER electrocatalysts,focus on their synthesis(post-treatment,in situ generation,and electrodeposition methods)and the enhancement of their electrocatalytic activity(via elemental doping,interface and vacancy engineering,construction of specific supports and nanostructures,and the design of bior polymetallic phosphides),and highlight the crucial issues and challenges of future development.
基金supported by the National Natural Science Foundation of China (21901088, 21901089, 22161021, 21971091)the Natural Science Foundation of Jiangxi Province(20192ACB20013)+1 种基金support of Jiangxi Province (jxsq2018106041)the “Young Elite Scientists Sponsorship Program” by CAST。
文摘It is critical to synthesize high-efficiency electrocatalysts to boost the performance of water splitting to meet the requirements of industrial applications. Metal-organic frameworks(MOFs) can function as ideal molecular platforms for the design of highly reactive transition metal phosphides(TMPs), a kind of candidates for high-efficiently electrocatalytic water splitting. The intrinsic activity of the electrocatalysts can be greatly improved via modulating the electronic structure of the catalytic center through the MOF precursors/templates. Moreover, the carbon layer converted in-situ by the organic ligands can not only protect the TMPs from being degraded in the harsh electrochemical environments, but also avoid agglomeration of the catalysts, thereby promoting their activities and stabilities. Furthermore,heteroatom-containing ligands can incorporate N, S or P, etc. atoms into the carbon matrixes after conversion, regulating the coordination microenvironments of the active centers as well as their electronic structures. In this review, we first summarized the latest developments in MOF-derived TMPs by the unique advantages in metal, organic ligand, and morphology regulations for electrocatalytic water splitting. Secondly, we concluded the critical scientific issues currently facing for designing state-of-the-art TMP-based electrocatalysts. Finally, we presented an outlook on this research area, encompassing electrocatalyst construction, catalytic mechanism research, etc.
基金supported by the State Key Laboratory of Catalytic Materials and Reaction Engineering(RIPP,SINOPEC)
文摘Thioetherification between mercaptan and diolefin is an efficient process to remove mercaptans in FCC gasoline at mild condition, during which the selective hydrogenation of diolefin to monoolefin is also expected. Here, Si O2 supported transition metal(Fe, Co, Ni, Mo and W) phosphides were tested for the thioetherification of isoprene and butanethiol on a fixed-bed reactor at 120℃ and 1.5 MPa H2, and their structure before and after reaction was characterized by means of XRD, HRTEM, N2 sorption, CO chemisorption, NH3-TPD, XPS and TG. It was found that, among different metal phosphides, Mo P/Si O2 showed the best performance, and the optimal nominal Mo P loading was 25%. Apart from the nature of metal, the density of metal and acid sites determined the catalyst performance. Metal site was mainly responsible for hydrogenation of isoprene, while acid site dominantly contributed to the thioetherification and the polymerization of olefins. Moreover, a balance between metallic and acidic functions is required to arrive at a desired performance. Excessive metal sites or acid sites led to the over-hydrogenation of isoprene or the severe polymerization of olefins, respectively. 25%Mo P/Si O2 was tested for 37 h time on stream, and butanethiol conversion maintained at 100%; although isoprene conversion remarkably decreased, the selectivity to isopentenes exceeded 80% after reaction for 11 h. We suggest that the deactivation of Mo P/Si O2 is mainly ascribed to the butanethiol poisoning and the carbonaceous deposit, especially the former.
基金supported by the National Natural Science Foundation of China(U1904215)Natural Science Foundation of Jiangsu Province(BK20200044)Changjiang scholars program of the Ministry of Education(Q2018270)。
文摘Metal-organic frameworks(MOFs)with high porosity and variable structure have attracted extensive attention in the field of electrochemistry,but their poor conductivity and stability have limited their development.Materials derived from MOFs can maintain the structural diversity and porosity characteristics of MOFs while improving their electrical conductivity and stability.Metal phosphides play an important role in electrochemistry because they possess rich active sites,unique physicochemical properties,and a porous structure.Published results show that MOF-derived metal-phosphides materials have great promise in the field of electrochemistry due to their controllable structure,high specific surface area,high stability and excellent electrical conductivity.MOF-derived metal-phosphides with significant electrochemical properties can be obtained by simply,economical and scalable synthetic methods.This work reviews the application of MOF-derived metal phosphides in electrochemistry.Specifically,the synthesis methodology and morphological characterization of MOFs derived metal-phosphides and their application in electrochemistry are described.Based on recent scientific advances,we discuss the challenges and opportunities for future research on MOF-derived metal-phosphides materials.
基金financially supported by the National Natural Science Foundation of China (Nos. 51725401, 51904030, and 21935006)
文摘Lithium−sulfur batteries are one of the most competitive high-energy batteries due to their high theoretical energy density of _(2)600 W·h·kg^(−1).However,their commercialization is limited by poor cycle stability mainly due to the low intrinsic electrical conductivity of sulfur and its discharged products(Li_(2)S_(2)/Li_(2)S),the sluggish reaction kinetics of sulfur cathode,and the“shuttle effect”of soluble intermediate lithi-um polysulfides in ether-based electrolyte.To address these challenges,catalytic hosts have recently been introduced in sulfur cathodes to en-hance the conversion of soluble polysulfides to the final solid products and thus prevent the dissolution and loss of active-sulfur material.In this review,we summarize the recent progress on the use of metal phosphides and borides of different dimensions as the catalytic host of sulfur cathodes and demonstrate the catalytic conversion mechanism of sulfur cathodes with the help of metal phosphides and borides for high-en-ergy and long-life lithium-sulfur batteries.Finally,future outlooks are proposed on developing advanced catalytic host materials to improve battery performance.
基金supported by the National Natural Science Foundation of China (nos. 21771012, 22038001, 51621003)。
文摘Exploring nonprecious electrocatalysts for water splitting with high efficiency and durability is critically important.Herein,bimetallic phosphides are encapsulated into graphitized carbon to construct a C@NiCoP composite nanoarray using bimetallic metal-organic framework(MOF) as a self-sacrificial template.The resulting C@NiCoP exhibits superior performance for pH-universal electrocatalytic hydrogen evolution reaction(HER),particularly representing a low overpotential of 46.3 mV at 10 mA cm^(-2) and Tafel slope of 44.1 mV dec^(-1) in alkaline media.The structural characterizations combined with theoretical calculation demonstrate that tailored electronic structure from bimetal atoms and the synergistic effect with graphitized carbon layer could jointly optimize the adsorption ability of hydrogen on active sites in HER process,and enhance the electrical conductivity as well.In addition,the carbon layer served as a protecting shell also prevents highly dispersed NiCoP components from agglomeration and/or loss in harsh media,finally improving the durability.This work thus provides a new insight into optimizing activity and stability of pH-universal electrocatalysts by the nanostructural design and electronic structure modulation.
基金National Natural Science Foundation of China (22202080,51872116, 12034002)the fellowship of China Postdoctoral Science Foundation (2022 M711296)the Jilin Province Science and Technology Development Program (20210301009GX)。
文摘Developing high-efficiency electrocatalysts for hydrogen evolution reaction(HER) and oxygen evolution reaction(OER) is required to enhance the sluggish kinetics of water dissociation and optimize the adsorption free energy of reaction intermediates.Herein,we tackle this challenge by incorporating high-valence Zr into CoP(ZrxCo_(1-x)P),which significantly accelerates the elementary steps of water electrolysis.Theoretical calculations indicate that the appropriate Zr incorporation effectively expedites the sluggish H2O dissociation kinetics and optimizes the adsorption energy of reaction intermediates for boosting the alkaline water electrolysis.These are confirmed by the experimental results of Zr_(0.06)Co_(0.94)P catalyst that delivers exceptional electrochemical activity.The overpotentials at the current density of 10 mA cm^(-2)(j10) are only 62(HER) and 240 mV(OER) in alkaline media.Furthermore,the Zr_(0.06)Co_(0.94)P/CC‖Zr_(0.06)Co_(0.94)P/CC system exhibits superior overall water splitting activity(1.53 V/j10),surpassing most of the reported bifunctional catalysts.This high-valence Zr incorporation and material design methods explore new avenues for realizing high-performance non-noble metal electrocatalysts.
基金Project supported by the National Key Research and Development Program of China(Grant No.2017YFB0701502).
文摘NiCo-based superalloys exhibit higher strength and creep resistance over conventional superalloys.Compositional effects on elastic properties of the γ and γ' phases in newly-developed NiCo-based superalloys were investigated by first-principles calculation combined with special quasi-random structures.The lattice constant,bulk modulus,and elastic constants vary linearly with the Co concentration in the NiCo solution.In the selected(Ni,Co)3(Al,W)and(Ni,Co)3(Al,Ti)model γ' phase,the lattice constant,and bulk modulus show a linear trend with alloying element concentrations.The addition of Co,Ti,and W can regulate lattice mismatch and increase the bulk modulus,simultaneously.W-addition shows excellent performance in strengthening the elastic properties in the γ' phase.Systems become unstable with higher W and Ni contents,e.g.,(Ni0.75Co0.25)3(Al0.25 W0.75),and become brittle with higher W and Co addition,e.g.,Co3(Al0.25 W0.75).Furthermore,Co,Ti,and W can increase the elastic constants on the whole,and such high elastic constants always correspond to a high elastic modulus.The anisotropy index always corresponds to the nature of Young's modulus in a specific direction.
基金supported by the National Natural Science Foundation of China(21875118,22179065,and 22105108)the Natural Science Foundation of Tianjin(19JCZDJC37700)+1 种基金the 111 project(B12015)China Postdoctoral Science Foundation(2020M680860)。
文摘Exploring feasible synthesis approaches to highly efficient and robust bifunctional electrocatalysts toward both oxygen evolution reaction(OER)and oxygen reduction reaction(ORR)is triggering researcher’s even-increasing interest in rechargeable Zn-air batteries.Herein,sulfur-doped bimetal FeCo phosphide nanoparticles dispersed on N,P,S-tri-doped graphene(donated as S-FeCo3P/NPSG)are rationally prepared through a controllable one-step carbothermal-phosphorization strategy.The modified charge distribution and electron-donor properties of S-FeCo3P/NPSG caused by S decoration render a significantly beneficial effect on the electrocatalytic activities.Consequently,the S-FeCo3P/NPSG electrode exhibits extraordinary bifunctional activities toward oxygen electrochemistry of the OER overpotential of 290 m V at 10 m A cm^(-2) and the ORR half-wave potential of 0.83 V,approaching to that of noblemetal IrO_(2)(289 m V)and Pt/C(0.84 V),respectively,but with more stronger operation stability in alkaline media.When S-FeCo3P/NPSG serves as the air cathode for liquid-state Zn-air battery,the large peak power density and energy density,as well as superb discharge-charge durability(cycling life>600 h)of this device are obtained.Furthermore,all-solid-state Zn-air battery with S-FeCo3P/NPSG as air electrode also displays excellent mechanical flexibility,high power density and stable cycling stability.The self-reconstruction behavior of the S-FeCo3P/NPSG cathode catalysts is also investigated during the electrocatalytic Zn-air battery operation.This work would provide some novel inspiration from aspects of bonding and charge distribution for the rational construction of active and cost-efficient bifucntional oxygen electrocatalysts for energy storage and conversion devices.
基金supported by the National Natural Science Foundation of China(21925206)the Strategic Priority Research Program of the Chinese Academy of Sciences(No.XDA 21000000)+1 种基金the National Key R&D Program of China(2020YFA0406100)the Liaoning provincial Natural Science Foundation of China(2020-BS-014)。
文摘Although conducting materials such as carbon nanotube and carbon fiber paper(CFP)have been extensively employed as support of electrocatalytic active sites,most of them are of poor catalytic functionality by themselves and undesirable stability during strong acid/alkaline environments or oxidation process.Here we report a novel one-dimensional(1D)nickel phosphide polymorphic heterostructure(denoted as NPPH)to work as one effective carbon-free functional support for loading of single-atom Ir water oxidation electrocatalyst.Specifically,the NPPH composed of both Ni12P5and Ni2P phases is not only active for robust alkaline water oxidation but also is of good stability and hydrophilicity for favorable loading of single-atom dispersed iridium.The NPPH supported single-atom Ir electrocatalyst(Ir/NPPH)is found to exhibit remarkably superior water oxidation activity with respect to the NPPH itself or CFP supported single-atom Ir catalyst(Ir/CFP),demonstrating the synergetic promotion effect between NPPH and single-atom Ir catalyst.Furthermore,the NPPH supported single-atom Ir catalyst can bear alkaline water oxidation for over 120 h at current density of 50 mA cm^(-2).The NPPH developed here is expected as functional support to composite with other water oxidation catalysts,as may be an alternative strategy of developing highly efficient carbon-free electrocatalysts.